CN103130389A - Method for removing endocrine disrupter in sludge by combining ultraviolet rays and hydrogen peroxide - Google Patents
Method for removing endocrine disrupter in sludge by combining ultraviolet rays and hydrogen peroxide Download PDFInfo
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- CN103130389A CN103130389A CN2013100689679A CN201310068967A CN103130389A CN 103130389 A CN103130389 A CN 103130389A CN 2013100689679 A CN2013100689679 A CN 2013100689679A CN 201310068967 A CN201310068967 A CN 201310068967A CN 103130389 A CN103130389 A CN 103130389A
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Abstract
The invention relates to a method for removing an endocrine disrupter in sludge by combining ultraviolet rays and hydrogen peroxide, which comprises the following steps: adjusting the pH value of the sludge to be treated with one liter containing 10<-3>-10 milligrams of endocrine disrupter, then adding hydrogen peroxide, wherein the dosage of hydrogen peroxide is characterized in that each liter of the sludge to be treated adds 0.01-5 mole of hydrogen peroxide, uniformly stirring, using an ultraviolet lamp with radiation wavelength of 253.7 nanometers for ultraviolet irradiation, wherein the irradiation strength is 0.05-0.08 milliwatts uare centimeter, detecting the endocrine disrupter in sludge after 1-20 minutes, wherein the removal rate is 60-90%. The method for removing the endocrine disrupter in sludge by combining ultraviolet rays and hydrogen peroxide has the advantages of simple and easy operation, mild reaction condition, short treatment time, high degradation rate on the endocrine disrupter, no secondary pollution, good resource utilization of the sludge, and large industrial application and prospect.
Description
Technical field
The present invention relates to the method for endocrine disrupter in a kind of ultraviolet ray and hydrogen peroxide combined removal mud.The method can be removed the endocrine disrupter in mud quickly and efficiently, reduces the environmental hazard of the mud that contains endocrine disrupter, is conducive to the follow-up recycling of mud.
Background technology
Endocrine disrupter refers to a class exogenous compounds, the list of the endocrine disrupter in physical environment is very long, comprises the compounds such as metabolite, organochlorine pesticide, dihydroxyphenyl propane, polychlorobiphenyl, phthalate and organotin of natural estrogen and synthetic estrogen, plant or mushroom oestrogenic hormon, alkylphenol polyoxyethylene.After this compounds enters body, can disturb the processes such as synthetic, release, running, metabolism, combination of normal secretion matter in body, activate or inhibition endocrine system function, destroy the material of keeping organism stability and regulating and controlling effect in endocrine system, disturb the mankind or all too many levels of animal endocrine system, and then cause anomalous effect.
Integrative development along with world economy, environment incretion interferent contacts with the environmental organism system that comprises the mankind in all directions by surrounding mediums such as food, water, atmosphere and soil, become " third generation pollution " of be badly in need of administering the beginning of this century, it may bring potential harm to ecotope and human health and existence.Environment incretion is comparatively general at occurring in nature, endanger also larger, even (every liter of nanogram) also can produce very large impact to biology under extremely low concentration, cause biological and human body sex hormone secretion amount and actively descend, sperm quantity reduces, reproductive organ is abnormal, and reproductive performance is reduced, offspring's health and surviving rate descend, the sickness rate of various cancers increases, some animals female phenomenons are serious, secondly also can cause some neurotoxicities and immunotoxicity.The existence of environment incretion interferent and the hazardness of humans and animals has all been obtained in various degree confirmation, environment incretion interferent also more and more receives global concern to the impact of the mankind and animal endocrine system, becomes the focus of international research.Therefore environmental behaviour and the Study on degradation of endocrine disrupter have very important significance to strategy of sustainable development tool.
The relative mud medium of endocrine disrupter is fairly simple owing to detecting in the sewage medium, and is therefore very fast about the removal researchdevelopment of endocrine disrupter in sewage.Studies show that, due to the effect of microbiological deterioration endocrine disrupter be because of the kind of endocrine disrupter different, the part endocrine disrupter has the characteristic of difficult for biological degradation, and microorganism is had certain selectivity, generally be difficult to find a kind of to all endocrine disrupters effective microbial strains all.From the chemical plant emission relevant to endocrine disrupter sewage or mud out, wherein endocrine disrupter and concentration of intermediate products are large for those, are difficult to directly process with biodegradable method.In sewage, the degradation method of endocrine disrupter mainly contains the senior method for oxidation such as photodegradation, ozone oxidation, Fenton oxidation at present.
Have some endocrine disrupters to have very strong hydrophobicity, they easily are adsorbed on mud after entering urban sewage treatment system, can not effectively be removed.The excess sludge that sewage work discharges or industrial sludge become a source greatly of endocrine disrupter in environment.But what be different from sewage is that sludge components is complicated, can cause interference to the analyzing and testing of endocrine disrupter wherein, so in mud, the removal progress of endocrine disrupter is slow.The at present relevant research of endocrine disrupter in mud only is confined to a few sludge handling process such as alkali stabilization, sludge aerobic and anaerobic digestion, composting, and existing studies show that, the methods such as mud alkali stabilization, anaerobic digestion, centrifuge dehydration, freeze-thaw, iron(ic) chloride conditioning, lime conditioning, polymkeric substance conditioning all can not the Endocrine chaff interference curing and remove and produce positive influence, even also can cause the mineral bound Hg of endocrine disrupter and persistence to strengthen.
What oneself carried out is a small amount of about studies show that sludge pretreatment Endocrine chaff interference is removed, the ozone pre-treatment has improved the effect to polycyclic aromatic hydrocarbons biological degradability in the anaerobic sludge digestion process; Oestrogenic hormon, nonyl phenol and the dihydroxyphenyl propane on mud can be effectively removed in the ozone pre-treatment; Based on alkaline hydrolysis, pyrolysis method and ozone pre-treatment are less to excess sludge anaerobic digestion process Chinese traditional medicine and personal hygiene article and estrogenic removal effect, and the ozone pre-treatment only has promoter action for the removal of some drugs.Therefore from removing the angle of endocrine disrupter, chemical advanced oxidation is a kind of desirable sludge pretreatment technology.But there is no study tour ultraviolet/hydrogen peroxide coupling technique to the removal of endocrine disrupter in mud.
Summary of the invention
The object of the present invention is to provide a kind of simple for process, reaction temperature and, the treatment time is short, the degradation rate of Endocrine chaff interference is high, the method for endocrine disrupter in the large removal mud of non-secondary pollution and industrial applications prospect.
For achieving the above object, the technical solution used in the present invention is: first detect the content of endocrine disrupter in pending mud, the content of endocrine disrupter is 10 in every liter of pending mud
-3During-10 milligrams of mass concentrations, the pH value that will contain the pending mud of endocrine disrupter is adjusted into 1-7, then add hydrogen peroxide in pending mud, the dosage of hydrogen peroxide is that every liter of pending mud adds 0.01-5 mole of hydrogen peroxide, again the ultraviolet lamp radiation wavelength is chosen to be 253.7 nanometers, exposure intensity is every square centimeter of 0.05-0.08 milliwatt, irradiation time is 1-20 minute, detect at last the endocrine disrupter content discovery in mud, the endocrine disrupter clearance in mud is 60-90%.
The present invention has following advantage:
1, the present invention adds hydrogen peroxide in the mud that contains endocrine disrupter, and temperature of reaction is not limit, and the initial pH value of applicable mud is 1-7, and in mud, the concentration range of endocrine disrupter is 10
-3-10 milligrams every liter, add hydrogen peroxide under normal temperature and pressure, be aided with uv irradiating and get final product, therefore have applied widelyly, reaction conditions is simple.
2, with independent uv irradiating or only add hydrogen peroxide and just can produce the strong oxidizers such as hydroxyl radical free radical and compare, both couplings of the present invention, uv irradiating can promote hydrogen peroxide generation hydroxyl radical free radical faster and more, improve oxidation effectiveness, the mud that this method processing contains endocrine disrupter can reach the clearance more than 95%.
3, the present invention's hydrogen peroxide used cheaply is easy to get, and treating processes is simple and easy to do, and required time is short, and construction cost is low, has processing cost low, and the time is short, and than other strong oxidizers such as ozone, application prospect is better.
4, environmental friendliness.In the method for utilizing endocrine disrupter in ultraviolet hydrogen peroxide coupling technique oxidation removal mud of the present invention, hydrogen peroxide and UV-light can not cause secondary pollution to environment in concentration range used, be the Green Oxidant of generally acknowledging.Mud after processing does not contain harmful organism substantially, is conducive to the recycling of mud.
5, applicable target compound scope is wide.The present invention is applicable to contain the mud of following endocrine disrupter: Estrone (oestrone); 17 β-Estradiol (estradiol); 17 α-Ethinyl Estradiol (Ethinylestradiol); Estriol (trihydroxy-oestrin); Bisphenol A (dihydroxyphenyl propane); Nonyl Phenol (nonyl phenol), structural formula is as follows successively:
Description of drawings
Fig. 1 is that the pH of embodiment 1 is the clearance of oestrone in 3,5,7 mud
Fig. 2 is that the pH of embodiment 1 is the clearance of estradiol in 3,5,7 mud
Fig. 3 is that the pH of embodiment 1 is the clearance of Ethinylestradiol in 3,5,7 mud
Fig. 4 is that the pH of embodiment 1 is the clearance of trihydroxy-oestrin in 3,5,7 mud
Fig. 5 is that the pH of embodiment 1 is the clearance of dihydroxyphenyl propane in 3,5,7 mud
Fig. 6 is that the pH of embodiment 1 is the clearance of nonyl phenol in 3,5,7 mud
The clearance of oestrone in mud when Fig. 7 is the different amount hydrogen peroxide of adding of embodiment 2
The clearance of estradiol in mud when Fig. 8 is the different amount hydrogen peroxide of adding of embodiment 2
The clearance of Ethinylestradiol in mud when Fig. 9 is the different amount hydrogen peroxide of adding of embodiment 2
The clearance of trihydroxy-oestrin in mud when Figure 10 is the different amount hydrogen peroxide of adding of embodiment 2
The clearance of dihydroxyphenyl propane in mud when Figure 11 is the different amount hydrogen peroxide of adding of embodiment 2
The clearance of nonyl phenol in mud when Figure 12 is the different amount hydrogen peroxide of adding of embodiment 2.
Embodiment
Give further instruction below by example to the present invention, certainly, the present invention is not limited only to following embodiment.
Adopt the method for endocrine disrupter in ultraviolet ray/hydrogen peroxide coupling technique oxidation removal mud, at first the actual mud of Sewage Plant is fetched the rear solid phase extraction pre-treatment of using, detect again the content of six kinds of endocrine disrupters (oestrone, estradiol, trihydroxy-oestrin, Ethinylestradiol, nonyl phenol, dihydroxyphenyl propane) in initial mud with high performance liquid chromatography, again initial mud is packed as six parts, add respectively separately these six kinds of endocrine disrupters in six parts of initial mud, make the content of corresponding endocrine disrupter in every part of mud all reach every liter of mud and contain 1 milligram.Regulating every part of mud initial pH value is 3,5,7, add 0.5 mole of every liter of mud of hydrogen peroxide, stir, be 253.7 nanometers at radiation wavelength, exposure intensity is to shine under the ultraviolet lamp of every square centimeter of 0.069 milliwatt, and in every part of mud, the clearance of corresponding representative endocrine disrupter is seen Fig. 1-6.The clearance of endocrine disrupter reduces with the increase of pH value, use the solid phase extraction pre-treatment, detect again the content discovery of endocrine disrupter in mud with high performance liquid chromatography: after reacting 40 minutes, be 3 at pH, 5, under 7 condition, the clearance of trihydroxy-oestrin, estradiol, Ethinylestradiol, dihydroxyphenyl propane, oestrone all reaches more than 80% (sees Fig. 1-5), and the clearance of nonyl phenol reaches 60% above (see figure 6).
Embodiment 2
Operation steps according to above-described embodiment 1, every liter of mud adds the hydrogen peroxide of 0.01,0.05,0.2,0.5 mole, stir, be 253.7 nanometers at radiation wavelength, exposure intensity is to shine under the ultraviolet lamp of every square centimeter of 0.069 milliwatt, process initial pH and be the mud that every liter of mud of 7 contains 1 milligram of endocrine disrupter, react after 60 minutes, detect the content of corresponding representative endocrine disrupter (oestrone, estradiol, trihydroxy-oestrin, Ethinylestradiol, nonyl phenol, dihydroxyphenyl propane) in every part of mud.In every part of mud, the clearance of corresponding representative endocrine disrupter is seen Fig. 7-12.The clearance of endocrine disrupter increases and increases with the hydrogen peroxide dosage, when the hydrogen peroxide dosage is 0.5 mole every liter, oxide treatment through 10 minutes, the clearance of oestrone, estradiol, Ethinylestradiol, trihydroxy-oestrin, dihydroxyphenyl propane all reaches more than 90% (sees Fig. 7-11), and the clearance of nonyl phenol reaches more than 80% (sees Figure 12).
Claims (1)
1. the method for endocrine disrupter in a ultraviolet ray and hydrogen peroxide combined removal mud, it is characterized in that: first detect the content of endocrine disrupter in pending mud, the content of endocrine disrupter is 10 in every liter of pending mud
-3During-10 milligrams of mass concentrations, the pH value of pending mud is adjusted into 1-7, then add hydrogen peroxide in pending mud, the dosage of hydrogen peroxide is that every liter of pending mud adds 0.01-5 mole of hydrogen peroxide, again the ultraviolet lamp radiation wavelength is chosen to be 253.7 nanometers, exposure intensity is every square centimeter of 0.05-0.08 milliwatt, and irradiation time is 1-20 minute, detect at last the endocrine disrupter content in mud, the endocrine disrupter clearance in mud is 60-90%.
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Cited By (6)
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| CN104031949A (en) * | 2014-06-10 | 2014-09-10 | 同济大学 | Method for improving acid production quality and acetic acid proportion in anaerobic fermentation of residue active sludge |
| CN104140137A (en) * | 2014-08-20 | 2014-11-12 | 云南大学 | Method for removing EDCs (endocrine disrupting chemicals) from water body by ultraviolet or visible light source in combination with alkaline substances |
| CN104773908A (en) * | 2015-03-27 | 2015-07-15 | 天津大学 | Endocrine disruptor-containing pickling wastewater treatment apparatus and method thereof |
| CN105036291A (en) * | 2015-08-05 | 2015-11-11 | 同济大学 | Method for degrading smelly substance in water through oxidizing agent activated by ultraviolet light |
| CN107340264A (en) * | 2017-03-29 | 2017-11-10 | 宁波方太厨具有限公司 | Cleaning machine |
| CN111377580A (en) * | 2019-12-28 | 2020-07-07 | 湖南大学 | Method for effectively degrading endocrine interferon in sludge |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107340264A (en) * | 2017-03-29 | 2017-11-10 | 宁波方太厨具有限公司 | Cleaning machine |
| CN107340264B (en) * | 2017-03-29 | 2020-01-14 | 宁波方太厨具有限公司 | Cleaning machine |
| CN111377580A (en) * | 2019-12-28 | 2020-07-07 | 湖南大学 | Method for effectively degrading endocrine interferon in sludge |
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